Study on electrochemical behavior of Nano‐ZnO modified alkyd‐based waterborne coatings

A nano‐composite coating was formed using nano‐ZnO as pigment in different concentrations, to a specially developed alkyd‐based waterborne coating. The nano‐ZnO modified composite coatings were applied on mild steel substrate by dipping. The dispersion of nano‐ZnO particles in coating system was investigated by scanning electron microscopic and atomic force microscopic techniques. The effect of the addition of these nano‐pigments on the electrochemical behavior of the coating was investigated in 3.5% NaCl solution, using electrochemical impedance spectroscopy. Coating modified with higher concentration of nano‐ZnO particles showed comparatively better performance as was evident from the pore resistance (R_po) and coating capacitance (C_c) values after 30 days of exposure. In general, the study showed an improvement in the corrosion resistance of the nano‐particle modified coatings as compared with the neat coating, confirming the positive effect of nano‐particle addition in coatings. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fabrication of ZnO-functionalized polypyrrole microcomposite as a protective coating to enhance anticorrosion performance of low carbon mild steel

In the present work, PPy, ZnO, and polypyrrole/zinc oxide (PPy/ZnO) microcomposites (1, 2, and 5 wt%) were prepared and their properties have been tuned for anticorrosion applications on low carbon mild steel. The synthesized products: ZnO, PPy, and composites were characterized by various sophisticated analytical techniques such as XRD, FTIR, Raman, FESEM, EDX, UV–VIS, TGA, and BET. The band frequencies observed at 480 and 588 cm⁻¹ in FTIR spectrum correspond to stretching vibrations of Zn-O and N-H bonds, respectively, broadening of the bands in the composites indicate strong interactions between ZnO and PPy matrix. The potentiodynamic polarization study of PPy and PPy/ZnO composite was carried out in 3.5% NaCl solution to investigate the corrosion resistance efficiency. PPy/1 wt% ZnO (I_corr = 190 nA) composite coating on low carbon mild steel was observed to exhibit best corrosion protection property compared to PPy (121 μA), 2 and 5 wt% ZnO (242, 295 nA) composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48319.     

Effect of 1,1′‐dibenzyl‐4,4′‐bipyridyl dichloride (DBD) on charge‐conduction process and photovoltaic response of a polypyrrole (PPy) thin‐film device

The present communication deals with analysing the effect of 1,1′‐dibenzyl‐4,4′‐bipyridyl dichloride (DBD) substitution at the N‐position of 2,5‐polypyrrole (PPy), on electrical, impedance and photovoltaic properties. The thin‐film device was fabricated by sandwiching DBD‐substituted PPy between indium tin oxide (ITO) and aluminium (Al) electrodes. The formation of a Schottky barrier with Al and ohmic contact with ITO are explained in terms of p‐type semiconducting behaviour of DBD‐substituted PPy. In the low‐voltage region, Ohm's law is followed, while in the high‐voltage region, a space‐charge‐limited conduction (SCLC) controlled by the exponential‐trap distribution was observed. DBD substitution causes shifting of the Fermi level towards the valence‐band edge and an increase in charge‐carrier mobility. A remarkable change in dark electrical conductivity of the order of five has been observed in DBD‐substituted PPy. The electrical and impedance measurements of an ITO/PPy:DBD/Al device confirms the formation of a Schottky barrier at the DBD‐substituted PPy/Al interface. Additionally, it can be modelled by a simple equivalent circuit of two resistance–capacitance (RC) elements in series representing the bulk and a junction‐region. At low frequency, the device capacitance follows a pronounced voltage dependence. From a detailed analysis of the J–V and C–V characteristics, the ionized acceptor concentration (N_a), width of depletion layer (W) and potential barrier height (?_b) have been evaluated. We observed a significant enhancement in photocurrent on DBD substitution. The increase in photocurrent is explained by the efficient charge separation induced by the intermolecular transfer of photo‐excited electrons from PPy to DBD. The substitution also causes a reduction in the trapping centres in the material. © 2002 Society of Chemical Industry     

siRNA Modified with 2′‐Deoxy‐2′‐C‐methylpyrimidine Nucleosides

(2′S)‐2′‐Deoxy‐2′‐C‐methyluridine and (2′R)‐2′‐deoxy‐2′‐C‐methyluridine were incorporated in the 3′‐overhang region of the sense and antisense strands and in positions 2 and 5 of the seed region of siRNA duplexes directed against Renilla luciferase, whereas (2′S)‐2′‐deoxy‐2′‐C‐methylcytidine was incorporated in the 6‐position of the seed region of the same constructions. A dual luciferase reporter assay in transfected HeLa cells was used as a model system to measure the IC₅₀ values of 24 different modified duplexes. The best results were obtained by the substitution of one thymidine unit in the antisense 3′‐overhang region by (2′S)‐ or (2′R)‐2′‐deoxy‐2′‐C‐methyluridine, reducing IC₅₀ to half of the value observed for the natural control. The selectivity of the modified siRNA was measured, it being found that modifications in positions 5 and 6 of the seed region had a positive effect on the ON/OFF activity.     

Electrosynthesis of PAni/PPy coatings doped by phosphotungstate on mild steel and their corrosion resistances

Polyaniline/polypyrrole (PAni/PPy), polyaniline-phosphotungstate/polypyrrole (PAni-PW₁₂/PPy) and PAni/PPy-PW₁₂ have been successfully electrodeposited on mild steel (MS) by cyclic voltammetry in aqueous oxalic acid solutions. It was found that the incorporation of PW₁₂ enhanced the corrosion resistance of PAni/PPy coating. Moreover, in comparison to PAni-PW₁₂/PPy, PAni/PPy-PW₁₂ coating exhibited better corrosion resistance for mild steel. After immersion of 36 h in 0.1 M HCl, for instance, the polarization resistance of PAni/PPy-PW₁₂ coating reached 1695 Ω cm², more than those of both PAni/PPy and PAni-PW₁₂/PPy.     

Molybdate‐doped copolymer coatings for corrosion prevention of stainless steel

The polypyrrole and polyaniline copolymer coating (PPy‐PAni) and PPy‐PAni doped with sodium molybdate copolymer coating ( ) were synthesized on stainless steel by cyclic voltammetry. The effect of molybdate on the passivation of stainless steel was investigated by linear sweep voltammetry in 0.2 mol L^?1 of oxalic acid. The corrosion prevention performances of these copolymer coatings for stainless steel were investigated by linear sweep voltammetry, electrochemical impedance spectroscopy in 1 mol L^?1 of sulfuric acid, and potentiodynamic polarization in 0.1 mol L^?1 of hydrochloric acid. Copolymer coating doped with molybdate could accelerate the formation of the passive oxide film and have better corrosion prevention efficiencies than PPy‐PAni coating on stainless steel. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40602.     

Poly(glycidyl methacrylate‐co‐3‐thienyl‐methylmethacrylate) based working electrodes for hydrogen peroxide biosensing

BACKGROUND: Hydrogen peroxide biosensors based on Poly(glycidyl methacrylate‐co‐3‐thienylmethylmethacrylate)/ Polypyrrole [Poly(GMA‐co‐MTM)/PPy] composite film were reported. Poly(GMA‐co‐MTM) including various amounts of GMA and MTM monomers was synthesized via the radical polymerization. Enzyme horseradish peroxidase (HRP) was trapped in Poly(GMA‐co‐MTM)/PPy composites during the electropolymerization reaction between pyrrole and thiophene groups of MTM monomer, and chemically bonded via the epoxy groups of GMA. Analytical parameters of the fabricated electrodes were calculated and are discussed in terms of film electroactivity and mass transfer conditions of the composite films. RESULTS: The amount of electroactive HRP was found to be 1.25, 0.34 and 0.213 µg for the working electrodes of Poly(GMA_30%‐ co‐MTM_70%)/PPy/HRP, Poly(GMA_85%‐co‐MTM_15%)/PPy/HRP and Poly(GMA_90%‐co‐MTM_10%)/PPy/HRP, respectively. Optimal response of the fabricated electrodes was obtained at pH 7 and an operational potential of ? 0.35 V. It was observed that effective enzyme immobilization and electroactivity of the composite films could be changed by changing the ratios of GMA and MTM fractions of Poly(GMA‐co‐MTM) based working electrodes. CONCLUSION: The amount of electroactive enzyme increases with increasing MTM content of the final copolymer. High operational stabilities of the biosensors can be attributed to the strong covalent enzyme linkage via the epoxy groups of GMA due to preventing enzyme deterioration and loss. A more convenient microenvironment for mass transfer was provided for the electrodes by higher GMA ratios. It is observed that mass transfer is dominated by the mechanism of electron transfer to obtain effective sensitivity values. This work contributes to discussions clarifying the problems regarding the design parameters of biosensors. Copyright © 2011 Society of Chemical Industry     

Atom transfer radical polymerization of (R)‐2‐methacryloyloxy‐2′‐methoxy‐1,1′‐binaphthalene

Atom transfer radical polymerization (ATRP) of (R)‐2‐methacryloyloxy‐2′‐methoxy‐1,1′‐binaphthalene ((R)‐MAMBN) mediated by different amine ligands, copper(I) chloride and ethyl 2‐bromopropionate in different solvents, and reverse ATRP of (R)‐MAMBN were studied. It was shown that optically active polymers were obtained, with poor control of the molecular weights, and low polydispersities. Specific rotation of the polymers increased with increasing molecular weights. By comparison with (R)‐MAMBN, poly((R)‐MAMBN)s exhibits higher specific rotation and a positive Cotton effect. Copyright © 2003 Society of Chemical Industry     

Diphosphate coatings for protection of galvanized steel: quality control by impedance measurements

Galvanized steel surfaces can be protected against corrosion in natural waters by a superficial coating of zinc diphosphate, obtained by the partial oxidation of zinc in a solution containing diphosphate ions.Impedance measurements were used to study the improvement in corrosion protection resulting from this layer and to develop a quality control method. The mechanism of both anodic and cathodic processes remains the same in the presence of the coating as in its absence, so that the relationshipR _tI_corr=constant is valid (R _t is charge transfer resistance;I _corr is intensity of the corrosion current). Thereby, a protection factor, defined as the ratio of the corrosion currents in the absence and in the presence of the coating, can be estimated from the corresponding charge transfer resistances determined experimentally from impedance diagrams.Impedance data obtained on several test-pieces are in good agreement with the coating morphology, as shown by direct scanning electron microscope (SEM) observations, leading to a simple criterion for quality control.     

The corrosion protection of mild steel by single layered polypyrrole and multilayered polypyrrole/poly(5-amino-1-naphthol) coatings

Electrochemical synthesis of polypyrrole (PPy) and top coat of poly(5-amino-1-naphthol) (PANAP) on PPy films from oxalic acid solution was achieved on mild steel (MS) by cyclic voltammetry technique. The morphology and the structure of the films were investigated by scanning electron microscopy (SEM). The corrosion performance of this multilayer coating and single PPy coating were investigated in 3.5% NaCl solution by using open circuit potential (E_ocp)–time curves, polarization curves and electrochemical impedance spectroscopy (EIS). It was found that the multilayer PPy/PANAP coating could provide much better protection than single PPy coating for corrosion of MS. It was observed that corrosion performance of coatings was increasing with immersion period. This was explained by auto-undoping properties of PPy coatings during immersion in corrosive solution. The improved corrosion performance in the presence of PANAP top coat on PPy was explained by increase in barrier effect of bilayer films.     

Mica/polypyrrole (doped) composite containing coatings for the corrosion protection of cold rolled steel

Micas/polypyrroles (PPys) doped with molybdate, p-toluene sulfonate, dodecyl benzene sulfonate, and 2-naphthalene sulfonate composite pigments were synthesized by chemical oxidative polymerization and characterized in coatings for corrosion protection on cold rolled steel substrate by various electrochemical techniques. Synthesized composite pigments were characterized for morphology by scanning electron microscopy, which indicated physical formation of PPy on the surface of mica. Chemical composition of the composite pigments was analyzed by X-ray photoelectron spectroscopy which chemically confirmed doped PPy formation on the mica surface. Coatings were formulated at 20% pigment volume concentration (composite pigments or as-received mica pigment) and were applied on cold rolled steel substrate. Coatings were exposed to salt spray test conditions (ASTM B117) for 30 days and were periodically assessed for corrosion with electrochemical impedance spectroscopy (EIS), open circuit potential (OCP), and potentiodynamic polarization. EIS and circuit modeling results demonstrated higher coating resistance (R _c) for mica/PPy (doped) composite coatings as compared to as-received mica pigment containing coating after 30 days of salt spray exposure. Lower current density and more positive corrosion potential values were observed for mica/PPy (doped) composite coatings as compared to mica pigment-based coating in potentiodynamic polarization measurements, indicating improved corrosion protection for cold rolled steel substrate. OCP measurements revealed more positive values for mica/PPy (doped) composite coatings as compared to mica pigment-based coating suggesting superior corrosion protection for mica/PPy (doped) composites.     

Evaluation of corrosion resistance of polypyrrole/functionalized multi-walled carbon nanotubes composite coatings on 60Cu–40Zn brass alloy

Polypyrrole/multi-walled carbon nanotubes (PPy/MWCNT) and its carboxylic functionalized (PPy/MWCNT-COO⁻) composite films were successfully electropolymerized by cyclic voltammetry as protective coating against corrosion on 60Cu–40Zn brass alloy surface. It yielded to strongly adherent and smooth nanocomposite films. Kinetics of the corrosion protection was investigated in 3.5 wt% NaCl solutions by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests. The results showed that the presence of MWCNT in PPy coat considerably reduces the corrosion rate of 60Cu–40Zn brass alloy. The enhanced inhibition is most likely due to interaction between MWCNT and PPy. This in turn, improves the alloy passivation improvement and alters the permselectivity of the coating from anionic selectivity to the cationic selectivity. Moreover, PPy/MWCNT-COO⁻ functionalized nanocomposite provided higher corrosion resistance coating than PPy/MWCNT alone.     

Corrosion behavior of titania films coated by liquid‐phase deposition on AISI304 stainless steel substrates

Fouling deposition and localized corrosion on the heat‐transfer surfaces of the stainless steel equipments often simultaneously exist, which can introduce additional thermal resistance to heat‐transfer and damage heat‐transfer surfaces. It is a good anticorrosion way to coat a barrier layer of certain materials on the metal surface. In this article, the TiO₂ coatings with nanoscale thicknesses were obtained by liquid‐phase deposition method on the substrates of AISI304 stainless steel (ASS). The coating thickness, surface roughness, surface morphology, crystal phase, and chemical element were characterized with the film thickness measuring instrument, roughmeter, atomic force microscopy, field emission scanning electron microscopy, X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy analyzer, respectively. Corrosion behavior of the TiO₂ coatings was evaluated by potentiodynamic polarization, cyclic voltammograms scanning, and electrochemical impedance spectroscopy tests with the mixed corrosion solution composed of 3.5 wt. % NaCl and 0.05 M NaOH. It is shown that the TiO₂ coating is composed of the nanoparticles with smooth, crack‐free, dense, and uniform surface topography; the roughness of coating surface increases slightly compared with that of the polished ASS substrate. The anatase‐phase TiO₂ coatings are obtained when sintering temperature being varied from 573.15 to 923.15 K and exhibit better anticorrosion behavior compared with ASS surfaces. The corrosion current density decreases and the polarization resistance increases with the increase of the coating thickness. The corrosion resistance of the TiO₂ coatings deteriorates with the increase of the corrosion time. The capacitance and the resistance of the corrosion product layer between the interface of the ASS substrate and the TiO₂ coating are found after the corrosion time of 240 h. A corrosion model was introduced, and a possible new explanation on the anticorrosion mechanisms of the TiO₂ coating was also analyzed. The corrosion mechanism of the TiO₂ coating might comply with the multistage corrosion process. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1907–1920, 2012     

Optically Active 4‐Substituted (S)‐2‐Phenyl‐2‐oxazolines

(R)‐4‐Hydroxymethyl‐2‐phenyl‐2‐oxazoline (R)‐ 1 ) was prepared from (L)‐serine. The respective tosylate ((S)‐ 2 ) was converted into sulfides (S)‐ 4 and (S)‐ 5 , and sulfone (S)‐ 6 , useful starting materials for the elaboration of additional chiral centers. A previously reported [ α]_D ²⁵ value for (R)‐ 4 is corrected.     

Vinylferrocene copolymers based biosensors for phenol derivatives

BACKGROUND: Newly synthesized composite films of P(glycidyl methacrylate₈₅‐co‐vinylferrocene₁₅)/Poly(glutaraldehyde)/ Polypyrrole [P(GMA₈₅‐co‐VFc₁₅)/PGA/PPy] and Poly(3‐methylthienyl methacrylate₈₅‐co‐vinylferrocene₁₅)/Polypyrrole [P (MTM₈₅‐co‐VFc₁₅)/PPy] were used as matrices for tyrosinase based working electrodes. Direct covalent attachment of enzyme was carried out via the pendant epoxy groups of P(GMA₈₅‐co‐VFc₁₅) film, and the entrapment of enzyme was achieved for electrode containing P(MTM₈₅‐co‐VFc₁₅) film via electropolymerization of pyrrole in the presence of enzyme. The aim of the study is amperometric determination of various phenolics and investigation of the effect of interfacial interactions between enzyme and matrices on biosensor response. RESULTS: The lowest detection limit and the highest sensitivity for a P(GMA₈₅‐co‐VFc₁₅) based working electrode was found to be 0.113 µmol L^?1 for 4‐methoxyphenol, 40 nA (µmol L^?1)^?1 for pyrocatechol, respectively. Results showed that sensitivities were at least 8500–55000 times higher than the results in previous P(GMA‐co‐VFc) related studies. CONCLUSION: Facilitated electron transfer was achieved by means of mediator incorporated in conductive composites of VFc based redox copolymers. The effect was greater when enzyme was covalently bonded via epoxy groups due to the proximity of enzyme, mediator and electrode surface. Results showed that a multifunctional surface was provided on electrodes since the suggested copolymers could mediate an electrochemical reaction, and the multifunctional surface was capable of coating with conductive PPy. Copyright © 2011 Society of Chemical Industry     

A New Class of 3′‐Sulfonyl BINAPHOS Ligands: Modulation of Activity and Selectivity in Asymmetric Palladium‐Catalysed Hydrophosphorylation of Styrene

Palladium‐catalysed monophosphorylation of (R)‐2,2′‐bisperfluoroalkanesulfonates of BINOL (R^F=CF₃ or C₄F₉) by a diaryl phosphinate [Ar₂P(O)H] followed by phosphine oxide reduction (Cl₃SiH) then lithium diisopropylamide‐mediated anionic thia‐Fries rearrangement furnishes enantiomerically‐pure (R)‐2′‐diarylphosphino‐2′‐hydroxy‐3′‐perfluoralkanesulfonyl‐1,1′‐binaphthalenes [(R)‐ 8ab and (R)‐ 8g–j ], which can be further diversified by Grignard reagent (RMgX)‐mediated CF₃‐displacement [→(R)‐ 8c–f ]. Coupling of (R)‐ 8a–j with (S)‐1,1′‐binaphthalene‐2,2′‐dioxychlorophosphine (S)‐ 9 generates 3′‐sulfonyl BINAPHOS ligands (R,S)‐ 10a–j in good yields (43–82%). These new ligands are of utlility in the asymmetric hydrophosphonylation of styrene ( 1 ) by 4,4,5,5‐tetramethyl‐1,3,2‐dioxaphospholane 2‐oxide ( 2 ), for which a combination of the chiral ligands with either [Pd(Cp)(allyl)] or [Pd(allyl)(MeCN)₂]⁺/NaCH(CO₂Me)₂ proves to be a convenient and active pre‐catalyst system. A combination of an electron‐rich phosphine moiety and an electron‐deficient 3′‐sulfone moiety provides the best enantioselectivity to date for this process, affording the branched 2‐phenethenephosphonate, (−)‐iso‐ 3 , in up to 74% ee with ligand (R,S)‐ 10i , where Ar=p‐anisyl and the 3′‐SO₂R group is triflone.     

The structure and photocatalytic performances of mechanically synthesized poly(3′,4′‐ethylenedioxy‐2,2′:5′,2″‐Terthiophene)/Zno composites

Poly(3′,4′‐ethylenedioxy‐2,2′:5′,2″‐terthiophene)/ZnO(poly(TET)/ZnO) composites with the ratio of poly(TET) and nano‐ZnO from 3:1 to 1:3 were synthesized by hand grinding and ball milling methods, respectively. The photocatalytic activities of the composites were examined through the degradation processes of methylene blue (MB) solution under UV light irradiation, and the possible mechanism for the photocatalytic activity enhancement by synergetic effects between nano‐ZnO and poly(TET) was proposed. The results showed that the strong interactions between the poly(TET) and nano‐ZnO occurred in the case of ball milling method. The results also proved that the crystallinity of ZnO was not disturbed in both of methods, and the nano‐ZnO was uniformly distributed in polymer matrix in the case of ball milling method. The comparative studies showed that the addition of the nano‐ZnO could enhance the photocatalytic activities of the composites. The highest degradation efficiency (100%) at 3 h under UV light irradiation occurred in the case of poly(TET)/ZnO(1:1) synthesized by ball milling method. Furthermore, the nanocompsosite displayed higher photocatalytic activity than nano‐ZnO, which was due to the holes (h⁺) transferring from the valence band of ZnO to the polymer backbone and the adsorption of MB molecules in polymer matrix via π–π conjugation between MB and aromatic regions of the poly(TET). POLYM. COMPOS., 36:1597–1605, 2015. © 2014 Society of Plastics Engineers     

Production of (R)‐3′‐fluorophenylethan‐1‐ol by Trichothecium roseum isolate in a laboratory scale bioreactor

BACKGROUND: Enantiomerically pure, fluorinated compounds play an important role in medicinal chemistry. Trichothecium roseum strains were isolated for the production of (R)‐3′‐fluorophenylethan‐1‐ol. Biocatalytic production of optically active (R)‐3′‐fluorophenylethan‐1‐ol was achieved by asymmetric reduction of 3′‐fluoroacetophenone in a batch culture of Trichothecium roseum using ram horn peptone (RHP). The reaction conditions (pH, temperature and agitation) required to improve the conversion of 3′‐fluoroacetophenone and enantiomeric excess (ee) of (R)‐3′‐fluorophenylethan‐1‐ol were studied. RESULTS: The gram scale production of (R)‐3′‐fluorophenylethan‐1‐ol by the most effective biocatalyst, Trichothecium roseum EBK‐11 using RHP was carried out in a fermenter with 1 L working volume. The results showed that the yield with >99% ee of (R)‐3′‐fluorophenylethan‐1‐ol reached 77%. The concentration of (R)‐3′‐fluorophenylethan‐1‐ol at the end of 62 h fermentation was 2.70 g L^?1. CONCLUSION: An important chiral intermediate for the pharmaceutical industry using T. roseum EBK‐11 in submerged culture containing RHP from waste material was produced up to gram scale with excellent ee (99%). In this work, T. roseum fungus was used for the first time as a biocatalyst for efficient production of a chiral alcohol. Copyright © 2009 Society of Chemical Industry     

Protective properties of PPy‐Au nanocomposite coatings prepared by sonoelectrochemisty and optimized by the Taguchi method

The polypyrrole (PPy) and polypyrrole‐Au (PPy‐Au) nanocomposite films have been sonoelectrochemically synthesized on St‐12 steel electrodes using the galvanostatic technique. Experimental design according to the Taguchi method has been applied to optimize the factors on the synthesis of PPy‐Au nanocomposite coating. Three factors were used to design an orthogonal array L9: Synthesis time (t), Current density (I), and Concentration of HAuCl₄ (C). The synthesized Au nanoparticles during polymerization were characterized by Ultraviolet–visible (UV‐visible) spectroscopy. Characterization of the surfaces was done by scanning electron microscope (SEM), energy dispersive X‐ray spectrum (EDX), and atomic force microscope (AFM). The scanning electron microscopy (SEM) image of PPy shows a smooth surface while PPy‐Au nanocomposite film has a compact morphology. Moreover, energy dispersive X‐ray spectrum (EDX) is evidence for the incorporation of Au nanoparticles. The corrosion protection of coatings was investigated by open circuit potential (OCP) time trends, potentiodynamic polarization technique, and electrochemical impedance spectroscopy (EIS) in a NaCl 3.5% solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41087.     

Ethylene/1‐octadecene copolymerization using [η5:η1‐C5Me4‐4‐R1‐6‐R‐C6H2O]TiCl2 catalysts

Copolymerization of ethylene with 1‐octadecene was studied using [η⁵:η¹‐C₅Me₄‐4‐R₁‐6‐R‐C₆H₂O]TiCl₂ [R₁ = ^tBu (1), H (2, 3, 4); R = ^tBu (1, 2), Me (3), Ph (4)] as catalysts in the presence of Al(i‐Bu)₃ and [Ph₃C][B(C₆F₅)₄]. The effect of the concentration of comonomer in the feed and Al/Ti molar ratio on the catalytic activity and molecular weight of the resultant copolymer were investigated. The substituents on the phenyl ring of the ligand affect considerably both the catalytic activity and comonomer incorporation. The 1 /Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] catalyst system exhibits the highest catalytic activity and produces copolymers with the highest molecular weight, while the 2 /Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] catalyst system gives copolymers with the highest comonomer incorporation under similar conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011